CN105470491B - One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method - Google Patents

One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method Download PDF

Info

Publication number
CN105470491B
CN105470491B CN201510802762.8A CN201510802762A CN105470491B CN 105470491 B CN105470491 B CN 105470491B CN 201510802762 A CN201510802762 A CN 201510802762A CN 105470491 B CN105470491 B CN 105470491B
Authority
CN
China
Prior art keywords
coo
freeze drying
drying technique
lithium ion
ion battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510802762.8A
Other languages
Chinese (zh)
Other versions
CN105470491A (en
Inventor
何丹农
吴晓燕
张春明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Original Assignee
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai National Engineering Research Center for Nanotechnology Co Ltd filed Critical Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority to CN201510802762.8A priority Critical patent/CN105470491B/en
Publication of CN105470491A publication Critical patent/CN105470491A/en
Application granted granted Critical
Publication of CN105470491B publication Critical patent/CN105470491B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a kind of Freeze Drying Technique auxiliary micro emulsion method to prepare lithium cell negative pole material Mn2CoO4Method, n-butanol, cationic surfactant and epoxychloropropane are stirred to well mixed, its volume ratio is 10：0.5：0.1；Stoichiometrically soluble manganese salt and soluble cobalt are dissolved in deionized water, magnetic agitation, the salting liquid is added into homogeneous solution obtained above, freezed, vacuum, dried 10 24 hours, drying and calcining, obtain lithium cell negative pole material Mn2CoO4.Microemulsion method is advantageous to prepare the controllable nano-scale particle of size, and Freeze Drying Technique can make preparation have loose continuous shape structure, be advantageous to the refinement of particle in calcination process.The two is combined with that particle size is controllable, less nanometer Mn beneficial to preparing2CoO4Particle, the specific surface area of material is larger, is advantageous to improve the chemical property of material.

Description

One kind prepares lithium cell negative pole material using Freeze Drying Technique auxiliary microemulsion method Mn2CoO4Method
Technical field
The present invention relates to a kind of preparation method of lithium cell negative pole material, is aided in more particularly to a kind of Freeze Drying Technique micro- Newborn method prepares lithium cell negative pole material Mn2CoO4Method.
Background technology
With the development of society, lithium ion battery receives much concern.Lithium ion battery be it is ideal in the world at present can Rechargeable battery, it not only has the advantages that energy density is big, had extended cycle life, memory-less effect and pollution are small.With technology Progressive, lithium ion battery will be widely used in the fields such as electric automobile, Aero-Space and biological medicine, therefore, research and development Power is significant with lithium ion battery and associated materials.For power lithium ion battery, its key is to carry High power density and energy density, and what power density and energy density improved is electrode material at all, particularly negative material Improvement.
From the beginning of the nineties in last century, Japanese scientific worker have developed the carbon material of layer structure, and carbon material is most It is early to be studied by people and be applied to the material of lithium ion battery commercialization, be still everybody concern so far and the emphasis studied it One, but some defects be present in carbon negative pole material：During Battery formation, react to form SEI films with electrolyte, cause disappearing for electrolyte Consumption and relatively low coulombic efficiency first；During over-charging of battery, it may form Li dendrite at carbon electrodes precipitating metal lithium and cause Short circuit, temperature is caused to raise, battery explosion；In addition, diffusion coefficient of the lithium ion in carbon material is smaller, cause battery real Existing high current charge-discharge, so as to limit the application of lithium ion battery.
Mn2CoO4It is a kind of composite oxides of spinel structure, is a kind of wide variety of magnetic material, is commonly used for firing Expect battery material, lithium ion battery negative material can also be used as at present, there is higher Li by conversion and alloying reaction+ Storage volume.The material is considered as a kind of promising ion cathode material lithium.
The present invention prepares Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4, microemulsion method is advantageous to prepare big I The nano-scale particle of control, Freeze Drying Technique can make preparation have loose continuous shape structure, be advantageous in calcination process The refinement of grain.The two is combined with that particle size is controllable, less nanometer Mn beneficial to preparing2CoO4Particle, the specific surface area of material It is larger, be advantageous to improve the chemical property of material.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides one kind and prepares lithium using Freeze Drying Technique auxiliary microemulsion method Cell negative pole material Mn2CoO4Method.
One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method, its feature exists In this method concretely comprises the following steps：
（1）N-butanol, cationic surfactant and epoxychloropropane are added in beaker, stirred to well mixed, Wherein n-butanol：Cationic surfactant：The volume ratio of epoxychloropropane is 10：0.5：0.1；
（2）Stoichiometrically soluble manganese salt and soluble cobalt are dissolved in deionized water, magnetic agitation 10-30 Minute, to above-mentioned steps（1）The salting liquid is added in obtained homogeneous solution, then ultrasonic 10-30 minutes；
（3）By step（2）Obtained solution is transferred in culture dish, is covered with preservative film, is freezed, will be freezed at -80 DEG C Good sample is put into freeze drier, vacuumizes, and dries 10-24 hours, and dried sample is put into crucible, in Muffle furnace 600-850 DEG C of calcining 5-10 hour, obtain lithium cell negative pole material Mn2CoO4。
Described cationic surfactant is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, ten One kind or its combination in dialkyl dimethyl amine oxide.
Described soluble manganese salt is manganese acetate, manganese nitrate or manganese oxalate.
Described soluble cobalt is cobalt acetate, cobalt nitrate or cobalt oxalate.
The present invention prepares Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4, microemulsion method is advantageous to prepare big I The nano-scale particle of control, Freeze Drying Technique can make preparation have loose continuous shape structure, be advantageous in calcination process The refinement of grain.The two is combined with that particle size is controllable, less nanometer Mn beneficial to preparing2CoO4Particle, the specific surface area of material It is larger, be advantageous to improve the chemical property of material.Cycle life figure under 100mA/g charging or discharging current density, Mn2CoO4It is first Secondary specific discharge capacity is about 1277 mAh/g, after 50 circulations, Mn2CoO4Specific discharge capacity be about 300 mAh/g.And Preparation technology is easy, and cost is cheap, it is considered to be a kind of promising material.
Brief description of the drawings
Fig. 1 is embodiment 1Mn2CoO4The XRD of material；
Fig. 2 is the Mn of embodiment 12CoO4The chemical property figure of material.
Embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these Examples of implementation.
Embodiment one：
200ml n-butanols, 10ml cetyl trimethylammonium bromides and 2ml epoxychloropropane are added in beaker, stirred Mix to well mixed；0.02 mol manganese acetates and 0.01 mol cobalt acetates are dissolved in deionized water, the min of magnetic agitation 30, to It is above-mentioned, the uniform salting liquid is added in homogeneous solution, then 30 min of ultrasound；Solution is transferred in culture dish, use is fresh-keeping Membrane cover is good, is freezed at -80 DEG C, and the sample freezed is put into freeze drier, vacuumized, and dries 20 h, dried sample Crucible is put into, 700 DEG C of 10 h of calcining in Muffle furnace is sent into, obtains lithium cell negative pole material Mn2CoO4.Fig. 1 is Mn2CoO4Material XRD, the material correspond to JCPD#23-408, are square spinel structures；Fig. 2 is Mn2CoO4Material in 100mA/g discharge and recharges Cycle life figure under current density, Mn2CoO4First discharge specific capacity is about 1277mAh/g, after 50 circulations, Mn2CoO4 Specific discharge capacity be about 300mAh/g.
Embodiment two：
200ml n-butanols, 10ml DDAOs surfactant and 2ml epoxychloropropane are added to In beaker, stir to well mixed；0.02 mol manganese nitrates and 0.01 mol cobalt nitrates are dissolved in deionized water, magnetic agitation 30 min, the uniform salting liquid is added into above-mentioned homogeneous solution, then 30 min of ultrasound；Solution is transferred to culture dish It is interior, covered with preservative film, freezed at -80 DEG C, the sample freezed is put into freeze drier, vacuumized, dry 20 h, done Dry good sample is put into crucible, is sent into 750 DEG C of 5 h of calcining in Muffle furnace, obtains lithium cell negative pole material Mn2CoO4。
Embodiment three：
200ml n-butanols, 10ml hexadecyltrimethylammonium chlorides and 2ml epoxychloropropane are added in beaker, stirred Mix to well mixed；0.02 mol manganese nitrates and 0.01 mol cobalt nitrates are dissolved in deionized water, the min of magnetic agitation 30, to The uniform salting liquid is added in above-mentioned homogeneous solution, then 30 min of ultrasound；Solution is transferred in culture dish, uses preservative film Cover, freezed at -80 DEG C, the sample freezed is put into freeze drier, vacuumized, dry 24 h, dried sample is put Enter crucible, be sent into 800 DEG C of 5 h of calcining in Muffle furnace, obtain lithium cell negative pole material Mn2CoO4。
Example IV：
200ml n-butanols, 10ml hexadecyltrimethylammonium chlorides and 2ml epoxychloropropane are added in beaker, stirred Mix to well mixed；0.02 mol manganese acetates and 0.01 mol cobalt acetates are dissolved in deionized water, the min of magnetic agitation 30, to The uniform salting liquid is added in above-mentioned homogeneous solution, then 30 min of ultrasound；Solution is transferred in culture dish, uses preservative film Cover, freezed at -80 DEG C, the sample freezed is put into freeze drier, vacuumized, dry 24 h, dried sample is put Enter crucible, be sent into 850 DEG C of 5 h of calcining in Muffle furnace, obtain lithium cell negative pole material Mn2CoO4。

Claims (4)

1. one kind prepares lithium ion battery negative material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method, it is special Sign is that this method concretely comprises the following steps：
（1）N-butanol, cationic surfactant and epoxychloropropane are added in beaker, stirred to well mixed, wherein N-butanol：Cationic surfactant：The volume ratio of epoxychloropropane is 10：0.5：0.1；
（2）Stoichiometrically soluble manganese salt and soluble cobalt are dissolved in deionized water, magnetic agitation 10-30 minutes, Uniform mixing salt solution is made, afterwards to above-mentioned steps（1）The mixing salt solution, Ran Houchao are added in obtained homogeneous solution Sound 10-30 minutes；
（3）By step（2）Obtained solution is transferred in culture dish, is covered with preservative film, is freezed at -80 DEG C, by what is freezed Sample is put into freeze drier, vacuumizes, dry 10-24 hours, dried sample is put into crucible, after Muffle 600-850 DEG C of calcining 5-10 hour, obtains lithium ion battery negative material Mn in stove2CoO4。
2. a kind of according to claim 1 prepare lithium ion battery negative material using Freeze Drying Technique auxiliary microemulsion method Mn2CoO4Method, it is characterised in that described cationic surfactant be cetyl trimethylammonium bromide, cetyl One kind or its combination in trimethyl ammonium chloride, DDAO.
3. a kind of according to claim 1 prepare lithium ion battery negative material using Freeze Drying Technique auxiliary microemulsion method Mn2CoO4Method, it is characterised in that described soluble manganese salt is manganese acetate or manganese nitrate.
4. a kind of according to claim 1 prepare lithium ion battery negative material using Freeze Drying Technique auxiliary microemulsion method Mn2CoO4Method, it is characterised in that described soluble cobalt is cobalt acetate or cobalt nitrate.
CN201510802762.8A 2015-11-19 2015-11-19 One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method Active CN105470491B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510802762.8A CN105470491B (en) 2015-11-19 2015-11-19 One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510802762.8A CN105470491B (en) 2015-11-19 2015-11-19 One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method

Publications (2)

Publication Number Publication Date
CN105470491A CN105470491A (en) 2016-04-06
CN105470491B true CN105470491B (en) 2018-04-03

Family

ID=55607985

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510802762.8A Active CN105470491B (en) 2015-11-19 2015-11-19 One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method

Country Status (1)

Country Link
CN (1) CN105470491B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106567156B (en) * 2016-11-08 2019-06-18 华南理工大学 The silica three-dimensional fiber material and preparation method thereof of cobalt load
CN109534406A (en) * 2018-11-21 2019-03-29 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of electrode material ferrous acid europium and products thereof and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9452475B2 (en) * 2012-03-01 2016-09-27 Bloom Energy Corporation Coatings for SOFC metallic interconnects
CN103996841B (en) * 2014-05-16 2016-06-15 上海纳米技术及应用国家工程研究中心有限公司 Lithium ion battery negative material (Mn, Co)3O4And preparation method thereof
CN104022275B (en) * 2014-05-28 2016-04-27 上海纳米技术及应用国家工程研究中心有限公司 Freeze drying micro emulsion legal system is ready for use on the lithium titanate material of lithium cell negative pole
CN104332623A (en) * 2014-09-09 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery negative material manganese cobalt oxide

Also Published As

Publication number Publication date
CN105470491A (en) 2016-04-06

Similar Documents

Publication Publication Date Title
CN106887583B (en) A kind of positive electrode and its preparation method and application
CN102694167B (en) Modified lithium manganate positive pole material and preparation method thereof
CN104466099B (en) High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material
CN104112845B (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN106410199B (en) A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN104979542A (en) Modified lithium titanate composite material, preparation method and application thereof
CN107681147A (en) A kind of preparation method of solid electrolyte coating modification anode material for lithium-ion batteries and application
CN107394172A (en) Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof
CN108807963A (en) Lithium ion battery negative material, preparation method and all-solid-state battery
CN105680043A (en) Preparation of nano-ferric fluoride and application of nano-ferric fluoride to positive electrode of high-specific-capacity lithium ion battery
CN108899549A (en) Carbon coating TiO in situ2(B) preparation method and application of negative electrode material
CN105826550A (en) Preparation method of lithium manganate cathode material with ferri-containing compound coating
CN105914354A (en) Sodium-rich type titanium matrix layered solid solution electrode material for room-temperature sodium ion battery and preparation method
CN104766953B (en) Preparation method of titanium dioxide/iron oxide composite anode material
CN106340400B (en) A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof
CN107887601A (en) Preparation method of lithium ion battery negative material zinc-manganese oxygen and products thereof and application
CN108023071A (en) Preparation method of foamy graphite alkene nickel-loaded cobalt oxide negative material and products thereof and application
CN105470491B (en) One kind prepares lithium cell negative pole material Mn using Freeze Drying Technique auxiliary microemulsion method2CoO4Method
CN105006563B (en) Lithium ion battery anode active material Li2ZnTi3O8Preparation method
CN107381656A (en) A kind of preparation method of lithium ion battery negative material
CN103094557A (en) Preparing method for lithium ion cell anode material with surface coated with ZnO
CN107871860A (en) Preparation method using metatitanic acid lithium cladding manganese cobalt oxide and products thereof and application
CN108565454A (en) A kind of nickel lithium manganate cathode material and its preparation method and application of three-dimensional desert wave structure
CN106684347A (en) Polypyrrole-coated cobalt manganese oxide coaxial nanowire, and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant